EP3063477B1 - Electrochemical descaling by pulsed signal reversal - Google Patents

Electrochemical descaling by pulsed signal reversal Download PDF

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Publication number
EP3063477B1
EP3063477B1 EP14716428.9A EP14716428A EP3063477B1 EP 3063477 B1 EP3063477 B1 EP 3063477B1 EP 14716428 A EP14716428 A EP 14716428A EP 3063477 B1 EP3063477 B1 EP 3063477B1
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EP
European Patent Office
Prior art keywords
heating element
heater
liquid
counter electrode
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14716428.9A
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German (de)
English (en)
French (fr)
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EP3063477A1 (en
Inventor
Johannes Hotze Bernhard De Vries
Ytsen Wielstra
Bernardo Arnoldus Mulder
Nienke Cornelie DE VRIES-ARENTSEN
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Koninklijke Philips NV
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Koninklijke Philips NV
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Priority to PL14716428T priority Critical patent/PL3063477T3/pl
Publication of EP3063477A1 publication Critical patent/EP3063477A1/en
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D19/00—Details
    • F24D19/0092—Devices for preventing or removing corrosion, slime or scale
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H9/00—Details
    • F24H9/40—Arrangements for preventing corrosion
    • F24H9/45—Arrangements for preventing corrosion for preventing galvanic corrosion, e.g. cathodic or electrolytic means
    • F24H9/455—Arrangements for preventing corrosion for preventing galvanic corrosion, e.g. cathodic or electrolytic means for water heaters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/46135—Voltage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4614—Current
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46145—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46155—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C02F2209/055—Hardness
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00—Location of water treatment or water treatment device
    • C02F2307/10—Location of water treatment or water treatment device as part of a potable water dispenser, e.g. for use in homes or offices

Definitions

  • the invention relates to a method for heating a liquid, especially water, a (water) heating arrangement for applying such method, as well as to an electronic device comprising such (water) heating arrangement.
  • Water heating devices are applied in all kind of applications, such as steam irons, electric kettles, hot drink vending machines, etc.
  • a problem with such devices is that scale may form on the heating elements that are in contact with the water.
  • a steam generation device water is supplied to a part of the water infrastructure where it is heated, such as in the (external) boiler of a system iron, as a consequence of which scale may be formed. If the scale is not (periodically) removed clogging up may occur, as a result of which the performance of the steam generation device may decrease and, eventually, the steam generation device may not be fit to be used anymore.
  • Hard water containing significant amount of Ca 2+ and HCO 3 - (bicarbonate) may form scale (CaCO 3 ) upon temperature increase via the following chemical reaction: Ca(HCO 3 ) 2 ⁇ CaCO 3 + H 2 O + CO 2
  • WO2012011026 and WO2012011051 describe methods to prevent scaling using electrochemical methods.
  • WO2012011051 describes the features of the preamble of claims 1, 9 and 14.
  • heating elements such as a heatable wall or an immersion heater
  • electrochemical scale prevention and/or removal from an (aqueous) liquid such as water is proposed.
  • a principle could be to have two electrodes in the water connected with a DC power supply. At the anode (+ electrode) oxidation is taking place. At the cathode (- electrode) reduction is taking place; in practice this means that at the cathode water is reduced: 2H 2 O + O 2 + 4e - ⁇ 4OH -
  • anode When the anode is reactive it may be oxidized. For example metal anodes will dissolve unless very stable metal (Pt), certain transition metal oxides or carbon anodes are used. Calcified steel can be decalcified by applying a positive voltage but its effect is limited by the corrosion resistance of the metal making only small voltages / currents feasible.
  • Pt very stable metal
  • certain transition metal oxides or carbon anodes are used.
  • Calcified steel can be decalcified by applying a positive voltage but its effect is limited by the corrosion resistance of the metal making only small voltages / currents feasible.
  • such simple setup may remove scale from the water by depositing it on a cathode and keeping the (oxidation resistant) anode clean.
  • a drawback besides the need for corrosion resistant anode material, may be that the cathode needs to be cleaned at regular intervals.
  • scale i.e. calcium carbonate (“calc) formation
  • AC signal By continuous reversal of the signal the heating element is alternating an anode or cathode. This means that alternating acid and base is generated at the surface of the heating element effectively weakening the adhesion of scale on to the heating element.
  • the basic idea behind the AC signal is that corrosion is suppressed by preventing metal ions to move from the electrode into solution.
  • metal ions tend to leave the electrode into the water (corrosion).
  • the signal is sufficiently fast reversed the metal ions are pulled back to the electrode.
  • the reversal fast enough ions cannot escape the boundary layer at the metal surface and corrosion is prevented.
  • the second AC signal needs to have certain amplitude to be effective. That means that when for example the amplitudes of both AC signals are equal that at the peak of the low frequency signal the amplitude is modulated by the second frequency bringing it down to 0V in the minimum but doubles it at the maximum (see below). The doubling of the amplitude can then result again in corrosion in spite of the second AC signal being present that could have prevented this corrosion due to the peak amplitude exceeding corrosion threshold.
  • the invention provides a method for heating a liquid in a heater, wherein the heater comprises a heating element and a counter electrode, wherein the method comprises (i) heating the liquid in the heater by heating the heating element to a temperature in the range of 120-250 °C, and (ii) applying an AC potential difference (V) between the heating element and the counter electrode, wherein the AC potential difference varies with an AC frequency (f) in the range of 200-2500 Hz and has an amplitude, in the range of 1-5 V, and wherein the liquid flows in the heater between the heating element and the counter electrode.
  • V AC potential difference
  • the invention provides a method wherein during or after heating a liquid, the heating element is subject to a fluctuating potential difference, wherein this fluctuation has a relative high frequency, in the range of 200-2500 Hz (and while being in contact with a (hot) aqueous liquid, especially water).
  • the AC frequency is in the range of 400-2200 Hz, such as 600-2000 Hz.
  • scaling can substantially be prevented and/or removed and corrosion can be prevented.
  • alternating current AC
  • alternating acid and base will be formed at the electrodes. While scale is formed during heating it will substantially not adhere to the electrode walls as it is constantly dissolved and re-precipitated at the electrode surface.
  • the method can also be used to decalcify already calcified surfaces.
  • the mobility of ions depends on the temperature. In water heating systems operated at relative low power the mobility is relative low. When a heater is operated under pressure and at high power like for example in a (flow through) heater of e.g. an espresso coffee machine the mobility is relative high. It appears that the higher the operating temperature the more symmetric the electrical signal may be to be to prevent corrosion. An additional DC signal may be low or even zero when the heater is operated at high temperature. At high temperatures, such as equal to or over 120 °C (i.e. of the heating element that is in contact with the liquid), the signal may especially be relative symmetrical.
  • the signal will have a duty cycle close to 100%.
  • duty cycle is known in the art, and especially relates to the percent of time that an entity spends in an active state as a fraction of the total time under consideration. For instance, when an AC potential has a sinusoidal shape, and the signal follows this sine, the duty cycle is 100%. would however during 25% of the time the signal be zero, or e.g. have an opposite signal (to the situation wherein the signal would follow the sine), the duty cycle would be 75%.
  • especially the AC voltage is applied with a duty cycle of the pulse being e.g. ⁇ 95%, such as especially 100%.
  • especially only the AC voltage is applied, without further additions or tweaking.
  • especially the AC voltage that is applied is based on a single component (having the indicated frequency), with a duty cycle of 100%, and with a DC component ⁇ 0.2 V, especially 0 V.
  • the AC frequency (f) is the range of 500-1500 Hz, wherein the AC voltage has a sinusoidal character, and wherein the potential difference is in the range of 1-5 V, such as at least 1.2 V, like 1.5-5 V, such as especially 1.5-4 V.
  • the counter electrode may be configured as heating element.
  • the liquid may flow between two heating elements, which are both used as electrodes.
  • the method may comprise heating the heating element to a temperature in the range of 120-250 °C, like in the range of 140-200 °C. Under the conditions described herein, this may imply that water may be heated to a temperature in the range of about 80-110 °C, especially about 85-100 °C.
  • the heating element may especially be used to heat the liquid to a temperature close to the boiling temperature (of the liquid).
  • the liquid may be heated under elevated pressure, i.e. a pressure above 1 bar.
  • the liquid in contact with the heating element is (brought) at a pressure in the range of 1-12 bar, especially 1-10 bar. In some instance, the pressure may be in the range of 7-12 bar, like 7-10 bar.
  • the heater arrangement may further comprise a device configured to impose a pressure to the liquid, especially a pressure larger than 1 and equal to or below 12 bar, such as in the range of > 1 bar and ⁇ 10 bar, like e.g. 7-10 bar.
  • a device configured to impose a pressure to the liquid, especially a pressure larger than 1 and equal to or below 12 bar, such as in the range of > 1 bar and ⁇ 10 bar, like e.g. 7-10 bar.
  • the (hot) liquid has a temperature in the range of 0.25-20 °C less than the boiling temperature, such as 1-15 °C less than the boiling temperature.
  • the invention also involves a method wherein the liquid is heated with the heating element to a temperature in the range of 0.25-20 °C less than the boiling temperature, such as 1-15 °C less than the boiling temperature.
  • the liquid may flow along the heating element.
  • the method may further comprise flowing the liquid along the heating element, especially with a flow speed in the range of 1.5-10 ml/s, such as in the range of 2-3.5 ml/s or 4.5-7 ml/s.
  • the method may thus comprise flowing the liquid between the heating element and the counter electrode with a flow speed in the range of 1.5-10 ml/s, such as in the range of 3-6 ml/s, like 4-6 ml/s. Therefore, in an embodiment the heater is configured to flow the liquid between the heating element and the counter electrode.
  • the heater comprises a flow through heater, wherein the heating element encloses the counter electrode.
  • the heating element and the counter electrode have a mutual (shortest) distance in the range of 0.5-5 mm.
  • the heater comprises a flow through heater, wherein the counter electrode encloses the heating element.
  • both the heating element and counter electrode are configured to heat the liquid (the counter electrode thus comprising a second heating element).
  • AC signals that have a sinusoidal or triangular or block shape.
  • sinusoidal shaped AC signals may be of interest.
  • the AC voltage has a sinusoidal wave shape.
  • Application of the AC voltage may be before, during, or after heating of the (aqueous) liquid.
  • the AC voltage is applied during heating of the (aqueous) liquid.
  • the phrase "applying a AC voltage between the heating element and a counter electrode” and similar phrases relate to the embodiment(s) that the heating element and the counter electrode are both in contact with the (aqueous) liquid.
  • the phrase “applying a AC voltage between the heating element and a counter electrode” refers to “applying a AC voltage between the heating element and a counter electrode, while the heating element and the counter electrode are in contact with the (aqueous) liquid.
  • the phrase "in contact” include embodiments wherein at least part of the item is in contact.
  • at least part of the heating element or at least part of the counter electrode may be in contact with the (aqueous) liquid, respectively.
  • the heating element can be earthed (grounded).
  • the liquid is especially water (though other aqueous liquids may also be heated with the method and heater arrangement as described herein).
  • the method may be used for hard and soft water, especially for water having a water conductivity of preferably at least 100 ⁇ S/cm.
  • the heating element can be immersed directly in the water or be arranged as (part of a) wall of the heater. In both cases the heater element (wall) acts as electrode and is electrically connected to the counter electrode. The (surface of the) heating element is thus in contact with the (aqueous) liquid in the heater. This is herein also indicated by the phrase "wherein the heating element is in contact with the (aqueous) liquid". Note that the term heating element thus refers to that part (element) that is in contact with the (aqueous) liquid and provides (when using the heater to heat the (aqueous) liquid) the heat from the heater to the (aqueous) liquid.
  • heating element may thus not necessarily refer to the actual heat generation device that generates the heat, but refers to that part/element, that transfers the heat to the (aqueous) liquid.
  • heating element may also refer to a plurality of heating elements.
  • the heating element for heating the (aqueous) liquid herein preferably comprises one or more metal parts for heating the liquid or is essentially from metal, such as a steel wall or a steel immersion heater. Hence, the heating element is herein also indicated as metal heating element. On this metal of the heating element that is in contact with the (aqueous) liquid, scale may deposit.
  • the heating element for heating the (aqueous) liquid herein preferably comprises one or more steel parts for heating the liquid or is essentially from steel.
  • the heating element, or the part of the heating element in contact with the water is preferably made of steel (though other materials may also be possible).
  • the heating element is a steel heating element.
  • counter electrode may in an embodiment also refer to a plurality of counter electrodes. For instance, when more than one signal is applied, in principle different counter electrodes may be applied. In an embodiment, the applied signals are applied on separate counter electrodes wherein thus the counter electrode comprises a plurality of counter electrodes, and wherein the AC voltage is applied between the heating element and a first counter electrode, and wherein a second AC voltage is applied between the heating element and a further counter electrode. Especially when two or more AC signals are applied, it may be an option to use for each AC signal a different counter electrode.
  • the counter electrode may for instance be a stainless steel or a mixed metal oxide (MMO), a carbon based or a platinum electrode. Where the wall of the heater is used as counter electrode, preferably the counter electrode is of metal, more preferably of steel.
  • MMO mixed metal oxide
  • the counter electrode is of metal, more preferably of steel.
  • steel herein especially refers to stainless steel. Any grade of stainless steel can be applied. Preferably the steel contains both Cr and Ni (e.g. grade 304) while additional presence of small amounts of Mo is especially beneficial (e.g. grade 316 or higher).
  • the term “heater” is used to indicate a device that is arranged to heat a liquid, such as water.
  • the heater especially relates to a water heater.
  • the term “water heater” is used to indicate a device that is arranged to heat an (aqueous) liquid, such as water.
  • the term “water heater” (herein shortly indicated with “heater”) may for instance refer to a steam generation chamber (based on heating an (aqueous) liquid).
  • the heater may be of the flow through heater type.
  • the heater may for instance heat the (aqueous) liquid in an embodiment via a heat generation device connected to the heater wall, wherein the wall (which is in contact with the (aqueous) liquid), is the heating element (for heating the (aqueous) liquid), or may for instance in an embodiment heat via an element in the (aqueous) liquid, such as water, such as in the case of an immersion type of heater (in which the heating element is in contact with the (aqueous) liquid), etc. Different types of heating elements may be applied (at the same time).
  • the term "(water) heater” may also refer to a (closed) boiler arranged to produce steam, to a (closed) boiler arranged to produce heated water, to a flow through heater or to a steamer.
  • the heater arranged for heating an (aqueous) liquid is selected from the group consisting of a flow through heater (see also below), a flow through steamer, a heater for heating water and a heater for producing steam. Further, the heater may also be configured to provide heated water and steam. Included are also heater blocks where the heating element and e.g. the tube that carries the water are embedded in a block of aluminum.
  • Heating may be any heating at temperatures above room temperature, but especially refers to heating (of the (aqueous) liquid) above 50 °C, such as especially heating the (aqueous) liquid in the heater to a temperature of at least 85 °C.
  • the term heating may thus include bringing at elevated temperatures, boiling and/or producing steam.
  • the heater may be any heater, such as a heater of a steam generation device (e.g. as used for a pressurized steam generator (sometimes also indicated as system iron)) for providing steam, a water heater for providing hot drinking water like in a hot liquid vending machine (e.g. for making coffee, tea, cappuccino, or hot chocolate, etc.), an electric kettle, a coffee maker (drip filter), an espresso machine, a pad coffee machine, a boiler (for internal heating of a house (domestic boiler) or of an apartment, an office building), an industrial boiler etc.), a water heater arranged in a washing machine or in a dish washer, or a hot-water based weed killing device (or sprayer) (arranged to providing hot water to kill weed).
  • a steam generation device e.g. as used for a pressurized steam generator (sometimes also indicated as system iron)
  • a water heater for providing hot drinking water like in a hot liquid vending machine (e.g. for making coffee, tea, cappuccino,
  • the invention also provides an arrangement with which the method of the invention may be applied.
  • the invention therefore provides in an embodiment a (water) heater arrangement comprising a (water) heater arranged for heating an (aqueous) liquid, the (water) heater comprising a heating element to heat the (aqueous) liquid in the (water) heater, the heating element arranged to be in contact with the (aqueous) liquid, and an electrical power supply, arranged to apply the AC voltage between the heating element and a counter electrode.
  • the heater arrangement may execute the herein described method.
  • the invention further provides a (water) heater arrangement comprising a heater, arranged for heating a liquid, comprising a heating element to heat the liquid in the heater and a counter electrode, a flow unit configured to flow the liquid between the heating element and the counter electrode, and an electrical power supply configured to apply an AC potential difference between the heating element and the counter electrode, wherein the AC potential difference varies with an AC frequency (f) in the range of 200-2500 Hz and has an amplitude in the range of 1-5 V.
  • f AC frequency
  • the heater is configured to flow the liquid between the heating element and the counter electrode, and wherein the heater comprises a flow through heater, wherein the heating element encloses the counter electrode (see however also above).
  • Flow through heaters are amongst others described in WO2006/067695 and WO2010/055472 , which are incorporated herein by reference.
  • the invention provides an electronic device comprising such heating arrangement wherein the electronic device is arranged to produce heated water and/or steam.
  • the electronic device may in an embodiment be selected from the group consisting of an iron, a pressurized steam generator, a non-pressurized steam generator (sometimes also indicated as a garment steamer), a hot liquid vending machine, an electric kettle, a coffee maker (drip filter), an espresso machine, a pad coffee machine, a washing machine, a dish washer, and a hot-water based weed killing device (sprayer).
  • the hot liquid vending machine may e.g.
  • the invention especially further provides an electronic device for providing a beverage comprising a liquid at elevated temperature, the electronic device comprising a (water) heater arrangement as defined herein, wherein the electronic device is arranged to produce heated water and/or steam for the beverage.
  • a beverage may be coffee, thee, espresso, and hot chocolate.
  • the electronic device or vending machine may optionally also be able to produce one or more of an espresso macchiato, espresso con panna, caffé latte, flat white, caffé breve, cappuccino, caffé mocha, americano, latte macchiato, red eye, cafe du lait, ristretto, espresso dopio, cafe creme, pepresso, etc. etc.
  • the invention also provides the use of an AC potential difference between a heating element and a counter electrode both in contact with a hot liquid, wherein the AC potential difference varies with an AC frequency (f) in the range of 200-2500 Hz and has an amplitude in the range of 1-5 V, to prevent or reduce scaling of the heating element.
  • the herein defined AC voltage is preferably applied during heating of the (aqueous) liquid in the heater with the heating element. This may have the most impact in preventing and/or reduction of scaling on the heating element.
  • the method further includes a measurement of the conductivity of the (aqueous) liquid, and optionally of other parameters, and optionally controlling the AC voltage and optionally one or more other parameters in dependence of the measurement and a predefined relations between the conductivity (and the optional other parameters) and the AC voltage and optionally one or more other parameters.
  • One or more optional other parameters that may be measured may be selected from the group consisting of the temperature of the (aqueous) liquid, the pH of the (aqueous) liquid, the current that is running (between the heating element and the counter electrode), the voltage drop when connecting the two electrodes (i.e. the heating element and the counter electrode), etc.
  • the method may involve controlling one or more of the potential difference, and AC frequency (f), and optionally the duty cycle as function of one or more of (i) a current between the heating element and the counter electrode, and (ii) an electrical conductivity of the liquid.
  • the current between the heating element and the counter electrode is measured.
  • the current and/or the conductivity measurement(s) may give information about the chemical processes that occur.
  • the current density (i.e. between the heating element and the counter electrode) is in the range of 0.1-10 mA/cm 2 , especially 0.1-5 mA/cm 2 , such as especially 0.2-0.6 mA/cm 2 , when using a flat heating element or a spiral shaped heating element in a boiler system, or especially 0.2-5 mA/cm 2 for a flow through heater.
  • the electrical power supply can be any system that is able to generate an AC voltage.
  • one or more of the frequency of the AC, the peak to peak voltage of the AC, etc. are variable and controllable, for instance one or more may be controlled in relation to a parameter like electric conductivity of the liquid and/or temperature of the liquid, or the current that is running.
  • the term electrical power supply may in an embodiment also refer to a plurality of electrical power supplies. In principle, each voltage may be generated by a different electrical power supply.
  • the application of the voltage may be applied preferably permanently during the time the (aqueous) liquid is at elevated temperatures, but may in an embodiment also be applied periodically.
  • the voltage is applied before or after heating of the (aqueous) liquid.
  • best results are obtained when the voltage is applied at least during heating of the (aqueous) liquid.
  • the water conductivity is in the range of 100 - 50,000 ⁇ S/cm and the water temperature is in the range of 50 °C - boiling temperature; especially ⁇ 85°C.
  • substantially herein, such as in “ “substantially consists”, will be understood by the person skilled in the art.
  • the term “substantially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially may also be removed.
  • the term “substantially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%.
  • the term “comprise” includes also embodiments wherein the term “comprises” means "consists of'.
  • the invention further applies to an apparatus or device comprising one or more of the characterizing features described in the description and/or shown in the attached drawings.
  • the invention further pertains to a method or process comprising one or more of the characterizing features described in the description and/or shown in the attached drawings.
  • FIG 1a schematically depicts a (water) heater arrangement (“heater arrangement") 1 comprising a (water) heater (“heater”) 100, arranged for heating an (aqueous) liquid 20.
  • the (aqueous) liquid 20, especially water, is contained in the heater 100.
  • the heater 100 comprises a metal heating element 110 to heat the (aqueous) liquid 20 in the heater 100.
  • the heater arrangement 1 further comprises an electrical power 200 supply, arranged to apply a AC voltage between the heating element 110 and a counter electrode 120. By application of the voltage, the metal heating element 110 is protected against scaling and/or scaling formed may be removed.
  • Figure 1a schematically depicts an embodiment of a flow through heater (FTH), wherein the heater 100 is a heater through which the (aqueous) liquid 20 flows, while being heated.
  • FTH flow through heater
  • a heat generation device 115 is connected to the wall of the heater 100, and a rod within the heater is used as counter electrode 120.
  • the wall is connected to an generation device 115 to heat the wall and is preferably of (stainless) steel; the wall is in contact with the (aqueous) liquid (not depicted) and is thus used as heating element 110.
  • the counter electrode 120 may comprise a material as indicated in the description above for figure 1b .
  • the heating element (110) and the counter electrode (120) have a (mutual) distance (d2), which may e.g. be in the range of 0.5-5 mm.
  • the circumferential heating element and the counter electrode may be arranged the other way around, with the counter electrode enclosing the heating element (this embodiment is not depicted).
  • Figure 1b schematically depicts substantially the same embodiment as schematically depicted in figure 1a , but now in cross-sectional view.
  • Elements 115 heat wall of the heater 100. Therefore, the wall is indicated as heating element 110.
  • the wall is used as heating element 110, and is preferably of (stainless) steel.
  • the counter electrode 120 may comprise a material as indicated in the description above for figure 1b .
  • Fig. 1c schematically depicts an example of a vending machine as example of an electronic device 2.
  • Reference 300 indicates a beverage.
  • FIG. 2a schematically depicts two electrodes, like the heating element and the counter electrode. The electrodes are indicated with EL. When an AC voltage is applied, there will be surface charge SC formed, which changes in sign continuously because of the AC character. In the vicinity of the electrodes, there will be an electrical double layer, indicated with DL.
  • Fig. 2b shows a solution by way of reference, wherein a slow AC is modulated with a fast AC.
  • the second AC signal needs to have certain amplitude to be effective. That means that when for example the amplitudes of both AC signals are equal that at the peak of the low frequency signal the amplitude is modulated by the second frequency bringing it down to 0V in the minimum but doubles it at the maximum ( figure 2b ). The doubling (in this example) of the amplitude can then result again in corrosion in spite of the second AC signal being present that could have prevented this corrosion due to the peak amplitude exceeding corrosion threshold.
  • Fig. 2c schematically depicts different AC signals, with a) indicating a triangular wave signal, b) indicating a sinusoidal signal and c) indicating a block wave signal. The best results are obtained with the sinusoidal signal.
  • the heater arrangement 1 may further comprise a sensor (not depicted) to sense parameters like conductivity of the (aqueous) liquid, the temperature of the (aqueous) liquid, etc. Further, the heater arrangement 1 may further comprise a controller, to control the one or more features of the AC and the temporary sign change of the potential difference. The controller may control those one or more features in dependence of the one or more parameters and one or more predefined relations between the one or more parameters and the one or more features.
  • Total hardness is defined as 2.8 x 2 x [mmol/ltr Ca + mmol Mg/ltr].
  • Temporary hardness is defined as 2.8 x [mmol HCO 3 - /ltr].
  • the first series of examples are comparative examples. These examples show that not each AC signal leads to the desired results and that tweaking of an AC potential difference also does not always lead to the desired results.
  • a sinusoidal AC signal of 3V and 0.5Hz was applied across the two electrodes. Severe corrosion occurred at both electrodes.
  • the heater is schematically shown in the figures 1c and 1d .
  • the outer tube, first heating element 110 is a stainless steel tube with two heat generation devices 115 at both sides.
  • the outer tube has a 15 cm length and a 13 mm inner diameter Together, they in fact form one heating element, surrounded by aluminum, with which the liquid is in contact when the liquid flows through the tube.
  • the inner tube may also be of stainless steel, and had a larger diameter than schematically depicted in fig. 1c / 1d : as counter electrode 120 a stainless steel tube of 8mm diameter was inserted in the tube. Water was passed through the area between the two stainless steel tubes at a speed of 2.25 ml/sec; the pressure in the heater system was 6-10bar. Both the outer tube and the inner tube of the water heating system were connected electrically. A typical test cycle consisted of heating water for 70seconds and cooling down for 50 seconds. This cycle was repeated for 500 times.
  • Said (water) heater was used for testing the calcification by the two water types without any electrical signal applied across the two electrodes. In both cases especially the wall was fully calcified and a dense layer of scale was formed that was strongly adhering to the wall.
  • the heater consists of a stainless steel tube (316 grade), with an inner diameter of 13mm, functioning as electrode. Two heating elements are connected to the outside of the tube. Inside the steel tube a second tube is mounted (304 grade). The second tube has an outer diameter of 8mm and functions as the 2nd electrode. Water flows in between the two tubes.
  • a typical experiment consists of 500 cycles, where each cycle comprises heating 150ml of standard hard water to 100 degrees Celcius and an electrical signal applied across the electrodes. The water is heated and dispensed with 2.25ml/s at high pressure, between 6 and 10 bars, resembling espresso conditions.
  • One experiment corresponds to 1500 cups of espresso.
  • a sinusoidal AC signal with amplitude 2.8V and frequency 200Hz was applied across the two electrodes. Pitting corrosion at the outer tube and coloration of both electrodes occurred.
  • a sinusoidal AC signal with amplitude 2.8V and frequency 2000Hz was applied across the two electrodes. No corrosion occurred and no decalcification effect was observed.
  • a sinusoidal AC signal with amplitude 1.6V and frequency 1000Hz was applied across the two electrodes. No corrosion occurred and decalcification effect is limited.
  • a sinusoidal AC signal with amplitude 3.2V and frequency 1000Hz was applied across the two electrodes. Pitting corrosion occurred.
  • a block shaped AC signal with amplitude 1.6V and frequency 1000Hz was applied across the two electrodes. No corrosion; limited decalcification effect.
  • a block shaped AC signal with amplitude 2.0V and frequency 1000Hz was applied across the two electrodes. Both electrodes show coloration.
  • a block shaped AC signal with amplitude 2.8V and frequency 1000Hz was applied across the two electrodes. The results are less advantageous.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Control Of Resistance Heating (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Instantaneous Water Boilers, Portable Hot-Water Supply Apparatuses, And Control Of Portable Hot-Water Supply Apparatuses (AREA)
EP14716428.9A 2013-04-02 2014-03-20 Electrochemical descaling by pulsed signal reversal Active EP3063477B1 (en)

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PL14716428T PL3063477T3 (pl) 2013-04-02 2014-03-20 Elektrochemiczne usuwanie kamienia za pomocą odwrócenia sygnału impulsowego

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WO2014162245A1 (en) * 2013-04-02 2014-10-09 Koninklijke Philips N.V. Electrochemical descaling by pulsed signal reversal
CN105865034B (zh) * 2015-01-19 2020-03-20 青岛海尔智能技术研发有限公司 热水器及其控制方法
CN105865035B (zh) * 2015-01-19 2020-02-14 青岛海尔智能技术研发有限公司 热水器及其控制方法
CN105865017B (zh) * 2015-01-19 2020-10-20 青岛海尔智能技术研发有限公司 热水器
US10425991B2 (en) * 2016-08-12 2019-09-24 Ken Gen Energy, Llc Pulse energy generator system

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US10077907B2 (en) 2018-09-18
CN105051461A (zh) 2015-11-11
JP6499156B2 (ja) 2019-04-10
US20160047557A1 (en) 2016-02-18
RU2015146770A (ru) 2017-05-10
RU2656806C2 (ru) 2018-06-06
EP3063477A1 (en) 2016-09-07
ES2737422T3 (es) 2020-01-14
JP2016521440A (ja) 2016-07-21
WO2014162231A1 (en) 2014-10-09
PL3063477T3 (pl) 2019-11-29
RU2015146770A3 (ja) 2018-03-19

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